KR101747462B1 - Colored polyimide molded article, and process for production thereof - Google Patents

Abstract

A polyamic acid solution composition containing at least a solution of a polyamic acid obtained from a tetracarboxylic acid component and a diamine component and a coloring precursor or a polyimide solution composition containing a polyimide solution and a coloring precursor and then heat- And forming a colored polyimide molding.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored polyimide molded article and a colored polyimide molded article,

The present invention relates to a method for producing a colored polyimide molded article and a colored polyimide molded article obtained by the method.

In general, when a polymer molded article is colored, a dye or a pigment is used.

For example, Patent Document 1 discloses a method of forming a colored resin pattern by using a colored polyimide resin material in which a dye is incorporated in a polyamic acid, and then curing the resin by heat treatment. In this method, an aromatic diamine is added in advance to the colored polyimide resin material, Discloses a method of preventing color leaching of a colored resin pattern in which a dye is bonded to a polyimidated polymer matrix through an aromatic diamine by heat treatment.

Patent Document 2 discloses a colored polyimide film for coating an electronic part containing a coloring pigment to a resin component containing as a main component a polyimide resin obtained from an aromatic tetracarboxylic acid dianhydride, an aromatic diamine having an aliphatic linear chain, and a siloxane diamine .

Pigments and dyes each have one end. For example, the pigment is advantageous in terms of heat resistance, but it is difficult to uniformly disperse the pigment in the resin. The dye has an advantage that it is uniformly dispersed (or dissolved), but there is a problem that it is liable to be eluted from the resin due to the influence of a solvent or the like.

On the other hand, the polyimide porous film is used for a battery separator, a diaphragm for an electrolytic capacitor, dust collecting, microfiltration, separation, and various manufacturing methods are known.

For example, Patent Document 3 discloses a polyimide porous film having a through-hole having a diameter of about 0.01 to 10 mu m and a porous film laminated on a cast film of a polyamic acid varnish, followed by dipping in a poor solvent A method for producing a membrane is disclosed.

Japanese Unexamined Patent Application Publication No. 5-119212 Japanese Patent Application Laid-Open No. 2004-304024 Japanese Patent Application Laid-Open No. 11-310658

Usually, a polyimide molding such as a colored polyimide film is produced by kneading a polymer solution such as a pigment such as carbon black and a polyamic acid solution, and after molding, removing a solvent or the like and heating to precipitate the polymer. Further, when the molded article is a porous film, the surface of the porous film is also colored.

However, if the surface of the porous film is colored, the properties of the controlled porous film may be lost.

Further, pigments such as carbon black do not have solubility with the polymer solution, and a special kneading machine for modifying the surface of the pigment such as carbon black or performing sufficient kneading is required in order to obtain a uniform mixing and dispersion state , It requires enormous labor force for practical use. In addition, the obtained molded article is not easily obtained with excellent surface appearance, and it is necessary to determine the optimum conditions through trial and error in accordance with the combination of materials, molding conditions, and kneading conditions.

In addition, when a pigment such as carbon black is used, the production line is contaminated. Therefore, it is necessary to prepare a dedicated production line or disassemble all of the lines and thoroughly clean them. Thus, a great labor force and cost, A cleaning agent is required.

It is an object of the present invention to provide a method for producing a polyimide molded article colored with a black system without using a pigment or a dye such as carbon black for solving the above problem and a colored polyimide molded article obtained by the method .

The present invention relates to the following (1) and (2).

(1) A polyamic acid solution composition comprising at least a solution of a polyamic acid obtained from a tetracarboxylic acid component and a diamine component and a coloring precursor, or a polyimide solution composition comprising a polyimide solution and a coloring precursor, And heat-treating the formed polyimide molded body.

(2) A colored polyimide molded article obtained by the method described in (1) above.

According to the production process of the present invention, since a color precursor having compatibility with a polyamic acid solution or a polyimide solution and having a property of being colored in a black color system by heating to 250 DEG C or higher is used, (1) a special kneader is used (2) a colored polyimide molding having an excellent surface appearance can be obtained, and (3) the line cleaning after the production can be easily carried out .

The effects of the present invention will be described in more detail as follows.

Since the method for producing a colored polyimide molded article of the present invention uses a color precursor which is spontaneously pyrolyzed and carbonized regardless of the presence or absence of a polyamic acid in the thermal imidization step, a combination of the polyimide and its additive, That is, the degree of freedom in designing the material is large, and it is industrially very advantageous.

The dye and the pigment are most likely to be discolored by thermal decomposition under the conditions of the thermal imidization process and the material used. However, the color precursor used in the present invention is not limited to the thermal imidization process or the high temperature use The present invention using this color precursor is very advantageous industrially since it can be kept in an initial color without discoloring even in use at a long-term high temperature because the material is thermally decomposed and denatured into a carbide under environmental conditions.

Fig. 1 is a graph showing the change in the thermogravimetric reduction rate when the polyacrylonitrile copolymer is heated at a rate of 5 deg. C / min from room temperature under air atmosphere (Reference Example 1).

In the method for producing a colored polyimide molded article of the present invention,

(1) a step of molding a polyamic acid solution composition containing at least a polyamic acid solution obtained from a tetracarboxylic acid component and a diamine component and a coloring precursor, followed by heat treatment at 250 ° C or higher (first invention), and

(2) a step of forming a polyimide solution composition containing a polyimide solution and a coloring precursor, followed by heat treatment at 250 캜 or higher (second invention).

Further, in the first invention, when the colored polyimide formed article is a colored polyimide porous film, the method for producing the colored polyimide porous film of the present invention is characterized in that the film obtained by casting the polyamic acid solution composition, A step of immersing the porous polyamic acid film in a poor solvent of polyamic acid to prepare a porous polyamic acid film, and a step of heat-treating the porous polyamic acid film at 250 ° C or higher (third invention).

<First Invention>

The first invention is characterized by including a step of molding a polyamic acid solution composition containing at least a solution of a polyamic acid obtained from a tetracarboxylic acid component and a diamine component and a coloring precursor and then subjecting the solution to a heat treatment at 250 ° C or higher.

(Polyamic acid)

Polyamic acid is obtained by polymerizing a tetracarboxylic acid component and a diamine component. Polyamic acid is a polyimide precursor which can be opened to form polyimide by thermal imidization or chemical imidization.

As the tetracarboxylic acid component, a known tetracarboxylic acid component can be used, and a tetracarboxylic acid dianhydride is preferable.

Specific examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride Biphenyltetracarboxylic acid dianhydride such as water (a-BPDA), 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride; (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4 ' (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, p-phenylenebis P-biphenylene bis (trimellitic acid monoester acid anhydride), m-terphenyl-3,4,3 ', 4'-tetracarboxylic acid dianhydride, p-terphenyl- (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4- , 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) Naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 4,4 '- (2,2-hexafluoroisopropylidene) di Phthalic acid dianhydride and the like. Further, an aromatic tetracarboxylic acid such as 2,3,3 ', 4'-diphenylsulfone tetracarboxylic acid may also be used.

Among them, at least one aromatic tetracarboxylic acid dianhydride selected from biphenyltetracarboxylic acid dianhydride and pyromellitic dianhydride is particularly preferable, and biphenyltetracarboxylic acid dianhydride is preferably 3,3 ', 4,4'-biphenyl Tetracarboxylic acid dianhydride (s-BPDA) is more preferable.

The tetracarboxylic acid component may be used alone or in combination of two or more.

The diamine component is not particularly limited, and a known diamine component can be used. For example, (i) a benzene nucleus, a benzene diamine, (ii) a benzene nucleus, 2 diamines, (iii) a benzene nucleus, 3 diamines, (iv) a benzene nucleus, 4 diamines, and the like.

(i) Benzene nucleus Examples of one benzene diamine include 1,4-diaminobenzene (paraphenylenediamine), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene And the like.

(ii) Benzene nucleus Examples of the two amines include 4,4'-diaminodiphenylether (DADE), 3,4'-diaminodiphenylether, and 3,3'-diaminodiphenylether. Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) Sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,3 ' - diamino 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'- 4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'- Dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3- (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'- Phenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, and the like.

(iii) Benzene nucleus Examples of the three diamines include 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, (3-aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3 ' Benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) Benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) Benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, and the like.

(iv) Benzene nucleus Examples of the four diamines include 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis 3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [3- Phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, ) Phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- Bis [3- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- Bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- ] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, and the like.

Among them, an aromatic diamine is preferable, and at least one selected from benzene diamine, diaminodiphenyl ether and bis (aminophenoxy) benzene is more preferable, and preferable examples thereof include paraphenylenediamine, 3,3 Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether (DADE), 1,3-bis (3-aminophenyl) benzene, 1 Benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) Benzene, 1,4-bis (3-aminophenoxy) benzene, and the like.

These diamine components may be used alone or in combination of two or more.

As the combination of the tetracarboxylic acid component and the diamine component of the polyimide, from the viewpoints of mechanical properties, long-term heat resistance and flame retardancy,

(1) tetracarboxylic acid component containing as a main component a component selected from 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and pyromellitic dianhydride, preferably 70 mol of 100 mol% tetracarboxylic acid component % Or more, more preferably 80 mol% or more, and particularly 90 mol% or more of a tetracarboxylic acid component,

(2) a compound selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenylether (DADE), 3,4'-diaminodiphenylether, 3,3'- (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis , Preferably from 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more, of the diamine component in 100 mol% of the diamine component is preferable.

As a more specific combination of the acid component and the diamine component constituting the preferable polyimide,

(1) A process for producing (3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine or p-phenylenediamine and diaminodiphenyl ether Phenyl ether or 3,4'-diaminodiphenyl ether)

(2) 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and pyromellitic acid dianhydride, p-phenylenediamine or p-phenylenediamine and diaminodiphenyl ether (4, 4'-diaminodiphenyl ether or 3,4'-diaminodiphenyl ether)

(3) a combination of pyromellitic dianhydride with p-phenylenediamine and diaminodiphenyl ether (4,4'-diaminodiphenyl ether or 3,4'-diaminodiphenyl ether) And the like.

The polyimide obtained by these combinations is suitably used as a material for electronic parts such as printed wiring boards, flexible printed boards, TAB, COF tapes, cover sheets, and reinforcing sheets, and has excellent mechanical properties, Is preferable since it has excellent hydrolysis resistance, high pyrolysis initiation temperature and excellent flame retardancy.

(Preparation of polyamic acid solution)

The polyamic acid solution may be a solution obtained by polymerizing tetracarboxylic dianhydride and diamine in the presence of an organic polar solvent or a solution obtained by dissolving polyamic acid in an organic polar solvent.

The solvent is not particularly limited. Organic polar solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and the like are preferable.

The polyamic acid can be produced, for example, by polymerizing the tetracarboxylic acid component and the diamine component at approximately equimolar amounts. The polymerization temperature is preferably about 100 캜 or less, more preferably 80 캜 or less, still more preferably 0 to 60 캜, particularly preferably 20 to 60 캜, and the polymerization time is preferably about 0.2 Hour, more preferably 0.3 to 60 hours.

In the production of polyamic acid, an arbitrary molecular weight regulator may be added.

In carrying out the polymerization reaction of the polyamic acid, the solution viscosity may be appropriately selected depending on the purpose (coating, flexibility, etc.) to be used and the purpose of production. From the viewpoint of workability, the polyamic acid solution (polyimide precursor solution) preferably has a rotational viscosity measured at 30 DEG C of about 0.1 to 5000 poises, preferably 0.5 to 2000 poises, more preferably 1 to 2000 poises . Therefore, it is preferable that the polymerization reaction is carried out to the extent that the produced polyamic acid exhibits the viscosity as described above.

In carrying out the polymerization reaction of the polyamic acid, the concentration of the whole monomers in the solvent may be appropriately selected depending on the purpose of use and the intended purpose. For example, in the case of the polyamic acid solution, the concentration of the total monomers in the solvent is preferably 5 to 40 mass %, More preferably 6 to 35 mass%, and further preferably 10 to 30 mass%.

The polyamic acid can be used as long as it does not affect the present invention even if a part of the amic acid is imidized. That is, the polyamic acid may be partially thermally imidized or chemically imidized.

When the polyamic acid is thermally imidized, fine particles such as an imidization catalyst, an organic phosphorus-containing compound, an inorganic fine particle, and an organic fine particle may be added to the polyamic acid solution as needed. When the polyamic acid is chemically imidized, fine particles such as a chemical imidization agent, a dehydrating agent, an inorganic fine particle, and an organic fine particle may be added to the polyamic acid solution as needed. It is preferable to carry out the treatment under the condition that the coloring precursor does not precipitate even when the above components are mixed in the polyamic acid solution.

Examples of the imidation catalyst include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group or an aromatic heterocyclic compound . More specifically, it is preferable to use at least one compound selected from the group consisting of 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, Methylbenzimidazole and the like, benzimidazole such as N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5 -Substituted pyridine such as dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine and the like can be suitably used.

The amount of the imidization catalyst to be used is preferably about 0.01 to about 2 times, more preferably about 0.02 to about 1 times, equivalent based on the amount of the amidic acid unit of the polyamic acid. Use of an imidation catalyst is preferable because physical properties, particularly elongation and thermal resistance, of the obtained polyimide film are improved.

Examples of the organophosphorus compound include monocaproyl phosphate ester, monoctyl phosphate ester, monolauryl phosphate ester, monomyristyl phosphate ester, monocetyl phosphate ester, monostearyl phosphate ester, triethylene glycol monotreidyl ether Monophosphoric acid ester, mono-phosphoric acid ester of tetraethylene glycol monolauryl ether, monophosphoric acid ester of diethylene glycol monostearyl ether, dicaproyl phosphate ester, dioctylphosphoric acid ester, dicapryl phosphate ester, Di-stearyl phosphate ester, di-stearyl phosphate ester, tetraethylene glycol mono neopentyl ether di-phosphate ester, tri-ethylene glycol mono-tridecyl ether di-phosphate ester, tetraethylene glycol mono Lauryl ether diacrylate, diethylene glycol monostearyl ether diphosphate Requester may be mentioned phosphoric acid ester, or amine salts of these phosphoric acid esters and the like. Examples of the amine include ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, Butylamine, monoethanolamine, diethanolamine, triethanolamine, and the like.

Examples of the inorganic fine particles include inorganic oxide powders such as titanium dioxide powder in the form of fine particles, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder and zinc oxide powder, inorganic nitride powder such as silicon nitride powder on a fine particle, , And silicon carbide powder, and inorganic salt powder such as fine calcium carbonate powder, calcium sulfate powder, barium sulfate powder and the like. In order to uniformly disperse these inorganic fine particles, a known dispersing means can be applied

Examples of the organic fine particles include organic fine particles which are insoluble in a solvent and do not change even when heated to 250 DEG C or higher, and include polyimide particles, polyamide particles, and crosslinkable particles.

The imidization catalyst, organic phosphorus-containing compound, inorganic fine particles and organic fine particles may be used alone or in combination of two or more.

Examples of the chemical imidization agent include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethyl aniline, isoquinoline, pyridine, 2-methylpyridine, 3-methylpyridine, 4- And heterocyclic tertiary amines such as methylpyridine, imidazole and benzimidazole. Heterocyclic tertiary amines are preferred, and 3-methylpyridine, 4-methylpyridine, imidazole, benzimidazole, More preferable.

Examples of the dehydrating agent for water generated in accordance with the imidization reaction include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, aromatic acid anhydrides such as benzoic anhydride and phthalic anhydride, and the like. Aliphatic acid anhydrides are preferable, Acetic acid is more preferred.

(Color precursor)

In the present invention, the term "color precursor" means a precursor which is partially or fully carbonized by heat treatment at 250 ° C. or higher to produce a colored product.

The coloring precursor to be used in the present invention is uniformly dissolved in a polyamic acid solution or a polyimide solution and is subjected to heat treatment at 250 占 폚 or higher, preferably 260 占 폚 or higher, more preferably 280 占 폚 or higher, more preferably 300 占 폚 or higher, Preferably, it is preferably pyrolyzed by heat treatment in the presence of oxygen such as air at 250 DEG C or higher, preferably 260 DEG C or higher, more preferably 280 DEG C or higher, more preferably 300 DEG C or higher and carbonized to produce a colored product , And more preferably a black-based colored product, and a carbon-based coloring precursor is more preferable.

The coloring precursor may appear to be a carbide at the same time when heated, but it may contain other elements other than carbon in a systematic manner, and may include a disordered structure including a layer structure, an aromatic cross-linking structure, and tetrahedral carbon.

The carbon-based coloring precursor is not particularly limited, and examples thereof include polymers obtained from monomers including tar or pitch such as petroleum tar, petroleum pitch, coal tar and coal pitch, coke, acrylonitrile, ferrocene compounds (ferrocene and ferrocene derivatives) And the like. Among these, a polymer and / or a ferrocene compound obtained from a monomer containing acrylonitrile are preferable, and a polymer obtained from a monomer containing acrylonitrile is preferably polyacrylonitrile.

Ferrocene (C ₁₀ H ₁₀ Fe) is a di-π-cyclopentadienyl iron, which itself is carbonized by heating, but it is also believed to have an effect of promoting the carbonization of polyamic acid. As the ferrocene, for example, a commercially available product of Wako Junyaku Kogyo Co., Ltd. can be used.

The ferrocene derivative in the present invention refers to a di- [pi] -cyclopentadienyl iron complex and includes a variety of substituents bonded as a pendant group of cyclopentadienyl ring. For example, there may be mentioned bisindenyl iron (II) (dibenzferrocene), 1,1'-diacetylferrocene, 1,2-diacetylferrocene, 1,1-diferrocenylene, dimethylaminoethylferrocene, Peroxycarbonyl aldehyde,? -Ferrocene fatty acid, phenylcyclopentafelene, phenylcyclohexanone, and the like, as well as aromatic heterocyclic compounds such as benzoic acid, 1,1 '- (1,3-cyclopentylene) ferrocene, phenylcyclopentylferrocene, benzoylferrocene, acetylferrocene and the like. Heterocyclic &lt; RTI ID = 0.0 &gt; pi &lt; / RTI &gt;

(Polyamic acid solution composition)

The polyamic acid solution composition is a solution composition obtained by uniformly dissolving the coloring precursor in a polyamic acid solution. On the other hand, the polyamic acid solution composition is preferably a suspension or a transparent uniform solution.

The polyamic acid solution composition can be prepared by adding a coloring precursor to a polyamic acid solution and mixing them, a method of adding a coloring precursor to a solvent in advance of polymerization of the polyamic acid to polymerize it, a method of adding a coloring precursor during polymerization of the polyamic acid, . &Lt; / RTI &gt;

The blending amount of the coloring precursor contained in the polyamic acid solution composition, particularly the carbon-based coloring precursor, may be appropriately selected according to the aimed coloring amount, and the coloring precursor is preferably added in an amount of 1 to 60 parts by mass to 100 parts by mass of the obtained polyimide More preferably from 2 to 40 parts by mass, more preferably from 2 to 30 parts by mass, particularly preferably from 3 to 25 parts by mass, based on 100 parts by mass of the total amount of the composition. The coloring effect can be obtained even when blended in an amount of 60 parts by mass or more. However, depending on the kind of the coloring precursor, the film properties, particularly the mechanical properties, of the obtained colored polyimide molded article may be lowered.

<Second invention>

The second invention is characterized by including a step of forming a polyimide solution composition comprising a polyimide solution and a coloring precursor, followed by heat treatment at 250 캜 or higher.

(Preparation of polyimide / polyimide solution)

As the polyimide used in the second invention, a polyimide soluble in a solvent can be used at a molding temperature, and a tetracarboxylic acid component and a diamine component are selectively combined and polymerized in a solvent to obtain a polyimide soluble in a solvent .

The tetracarboxylic acid component and the diamine component constituting the polyimide are as described above, and the preferable combination of the tetracarboxylic acid component and the diamine component is as described above.

Examples of the solvent for polymerizing the polyimide include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N- dimethylformamide, dimethylsulfoxide, (NMP), N, N-dimethylacetamide (DMAc), phenol, p-chlorophenol, o-chlorophenol, cresol And the like are preferable.

The polyimide can be produced, for example, by polymerizing the tetracarboxylic acid component and the diamine component at approximately equimolar amounts. The polymerization temperature is preferably 130 占 폚 or higher, more preferably 150 to 250 占 폚, and still more preferably 170 to 230 占 폚. The polymerization time is preferably about 0.2 hour or more, 60 hours.

In the production of the polyimide, any molecular weight regulator may be added.

In carrying out the polymerization reaction of the polyimide, the solution viscosity may be appropriately selected depending on the purpose (coating, flexibility, etc.) to be used and the purpose of production. It is preferable that the polyimide solution has a rotational viscosity measured at a molding temperature of about 0.1 to 5000 poise, preferably 0.5 to 2000 poise, and more preferably 1 to 2000 poise, from the viewpoint of workability. Therefore, it is preferable that the polymerization reaction is carried out to the extent that the resulting polyimide exhibits the viscosity as described above.

In carrying out the polymerization reaction of polyimide, the concentration of the total monomers in the solvent may be appropriately selected depending on the purpose of use and the intended purpose. For example, the polyimide solution preferably has a concentration of 5 to 30 mass %, More preferably 6 to 25 mass%, and further preferably 10 to 20 mass%.

(Polyimide solution composition)

The polyimide solution composition is a solution composition obtained by uniformly dissolving the coloring precursor in a polyimide solution at a temperature during molding. On the other hand, the polyimide solution composition is preferably a suspension or a transparent uniform solution.

The polyimide solution composition may be prepared by a method in which a coloring precursor is added to a polyimide solution and mixed, a method in which a coloring precursor is added to a solvent in advance before polymerization of the polyimide, a method in which a coloring precursor is added during polymerization, . &Lt; / RTI &gt;

The blending amount of the coloring precursor contained in the polyimide solution composition may be appropriately selected according to the intended coloring amount, and the coloring precursor is preferably added in an amount of 1 to 60 parts by mass, more preferably 2 To 40 parts by mass, more preferably 2 to 30 parts by mass. The coloring effect can be obtained even when blended in an amount of 60 parts by mass or more. However, depending on the kind of the coloring precursor, the film properties, particularly the mechanical properties, of the obtained colored polyimide molded article may be lowered.

When the polyimide solution is thermally imidized, fine particles such as an imidization catalyst, an organic phosphorus-containing compound, an inorganic fine particle, and an organic fine particle may be added as needed. It is preferable that the treatment is carried out under the condition that the coloring precursor does not precipitate even when the above components are blended in the polyimide solution.

The imidization catalyst, organic phosphorus-containing compound, inorganic fine particles and organic fine particles are the same as described above, and they may be used alone or in combination of two or more.

&Lt; Molding of polyamic acid solution composition or polyimide solution composition >

In the first and second inventions, the method of forming the polyamic acid solution composition and the polyimide solution composition is not particularly limited and may be a film, a film, a sheet, a fiber, a tube, or the like Can be molded. More specifically, the following methods (i) to (iii) can be mentioned.

(i) A method of peeling a film or sheet from a substrate after the polyamic acid solution composition or the polyimide solution composition is plied on the substrate and the solvent is volatilized by heat drying or vacuum drying.

(ii) A method of obtaining a belt or a tube by cutting a film or a sheet-shaped formed body obtained by the method (i) or the like at predetermined lengths and widths and connecting them.

(iii) A polyamic acid solution composition or a polyimide solution composition is applied to the inner or outer surface of the cylindrical metal mold, the solvent is volatilized and heated or just peeled off, and the metal mold is inserted into the outer periphery of another mold for defining the inner diameter , And heating to obtain an endless belt or a tubular shaped body.

&Lt; Production of colored polyimide molded article (1) (molding, heat treatment) >

Specific examples of the method for producing the colored polyimide molded article using the polyamic acid solution composition include the following (1) and (2).

(1) A method in which a polyamic acid solution composition is formed into a film or the like, and heat treatment is performed at 250 캜 or higher and, if necessary, at a maximum heating temperature of 350 - 600 캜, while gradually removing part or all of the solvent to imidize and color.

(2) The polyamic acid solution composition is formed into a film or the like, and the molded product is heated to a temperature at which the coloring precursor is not colored, preferably 50 to 210 캜, more preferably 60 to 200 캜, (In the case of a film, it is pre-dried until it has a self-supporting property that can be peeled off from the support), and thereafter the temperature is 250 ° C or more, which is the temperature at which the coloring precursor is colored, Followed by heat treatment at a maximum heating temperature of 350 ° C to 600 ° C to perform imidization and coloring.

Examples of producing a film by thermal imidization from a polyamic acid solution composition include a method in which a polyamic acid solution composition is coated on a suitable support (for example, a roll made of a metal, a ceramic plastic, or a metal belt, Or belt) to form a film of a polyamic acid solution having a uniform thickness of about 10 to 2000 m, particularly about 20 to 1000 m. Subsequently, the solvent is gradually removed by heating at 50 to 210 DEG C, particularly 60 to 200 DEG C by using a heat source such as hot air or infrared rays, and a part of the polyamic acid is imidized to peel the support from the support, And the self-supporting film is peeled from the support.

Then, the peeled self-supporting film is heat-treated at a temperature of 250 占 폚 or more, preferably 280 to 600 占 폚, more preferably 310 to 590 占 폚, more preferably 320 to 580 占 폚, particularly preferably 350 to 500 占 폚 do.

The heat treatment time may suitably be selected from a combination of an acid component and a diamine component constituting the polyamic acid. The heat treatment can be carried out under a multi-stage condition. In the case of heating at 250 占 폚 or more, both ends or all the circumference of the film is fixed with a pin tenter, a clip or a frame, desirable. The heat treatment can be performed using various known devices such as a hot air furnace, an infrared heat furnace, and the like. The heating time can be appropriately selected, but is preferably 5 to 120 minutes, and more preferably 5 to 60 minutes. Imidation and / or coloring proceeds by this heat treatment.

The method can also be applied to a polyimide solution composition.

&Lt; Production of colored polyimide molded article (2) (molding, heat treatment)

Specific examples of the method for producing the colored polyimide molded article using the polyimide solution composition include the following (1) and (2).

(1) A method in which the polyimide solution composition is formed into a film or the like, and is subjected to heat treatment at 250 占 폚 or higher, preferably at a maximum heating temperature of 350 占 폚 to 600 占 폚, while gradually removing part or all of the solvent.

(2) The polyimide solution composition is formed into a film or the like, and the molded product is heated to a temperature at which the coloring precursor is not colored, preferably 50 to 210 캜, more preferably 60 to 200 캜, Is gradually dried until it becomes self-supporting, and is then subjected to heat treatment at a temperature of 250 DEG C or higher, preferably a maximum heating temperature of 350 DEG C to 600 DEG C, which is a temperature at which the coloring precursor is colored.

According to the production method of the present invention, a colored polyimide molded article in which the light shielding property is controlled can be efficiently obtained. This colored polyimide molded article can be used as a material for electronic parts or electronic devices such as a printed wiring board, a flexible printed board, a TAB tape, a COF tape, a cover film, a reinforcing film, Metal moldings, and the like.

<Third invention>

A process for producing a colored polyimide porous film according to a third aspect of the present invention comprises the steps of: dipping a film obtained by softening a polyamic acid solution composition into a poor solvent of polyamic acid to prepare a porous polyamic acid film; And a step of performing heat treatment as described above.

The polyamic acid solution composition used in the third invention is the same as the polyamic acid solution composition used in the first invention.

In the polyamic acid solution used in the third invention, the polyamic acid solution has an intrinsic viscosity (30 캜, concentration: 0.5 g / 100 mL, solvent: NMP) as long as the polyimide porous film of the present invention can be produced. In the method of the present invention, it is preferable to use a polyamic acid having an intrinsic viscosity of preferably 0.3 or more, more preferably 0.5 to 5, and still more preferably 0.5 to 7.

The concentration of the polymer contained in the polyamic acid solution used in the third invention is not particularly limited as long as the concentration is such that the polyamic acid porous material is obtained by contacting with a poor solvent to obtain a polyamic acid porous material. Preferably, the concentration of the polyamic acid (solid content concentration) And 40 to 99.7 mass% of an organic polar solvent. When the solid content concentration of the polyamic acid is less than 0.3 mass%, the film strength when the porous polyimide film is produced is lowered, and when it exceeds 60 mass%, the material permeability of the porous polyimide film is sometimes lowered. The solid content concentration of the polyamic acid in the polyamic acid solution used in the third invention is more preferably 1 to 40 mass%, more preferably 3 to 30 mass%, particularly preferably 5 to 15 mass%, and an organic polar solvent Is more preferably 60 to 99% by mass, still more preferably 70 to 97% by mass, and particularly preferably 85 to 95% by mass.

The coloring precursor used in the third invention is a compound that is uniformly dissolved in a polyamic acid solution and does not substantially dissolve in a poor solvent and is pyrolyzed by heat treatment at 250 ° C or higher, preferably heat treatment at 250 ° C or higher in the presence of oxygen such as air , It is preferable to carbonize to produce a colored product, more preferably to produce a black colored product, and more preferably a carbon-based coloring precursor.

Preferable specific examples of the coloring precursor used in the third invention are the same as preferred specific examples of the coloring precursor used in the first invention.

&Lt; Preparation of film of polyamic acid solution composition >

In the method for producing a porous polyimide of the present invention, first, the polyamic acid solution obtained above and the above-mentioned coloring precursor are mixed to prepare a polyamic acid solution composition in which the coloring precursor is uniformly dissolved in the polyamic acid solution, To form a film.

In the case of chemical imidization, the catalyst and the dehydrating agent are mixed with the polyamic acid solution composition, and the film is formed on the substrate by pliability on the substrate.

(softness)

The method of softening is not particularly limited, and the polyamic acid solution composition can be formed into a film shape on a substrate such as a glass plate or a stainless plate by using, for example, a T-die, a comma coater, a blade or the like. Further, the polyamic acid solution composition may be intermittently or continuously fused in a film form on a continuously moving type belt to continuously produce film pieces or elongated shaped films. The belt may be any material as long as it is not affected by the polyamic acid solution composition and the poor solvent described later, and may be made of a metal such as stainless steel or a resin such as polytetrafluoroethylene. Further, the polyamic acid solution composition formed into a film shape may be directly introduced into a poor solvent. Further, one side or both sides of the obtained film material may be brought into contact with a gas (air, inert gas, etc.) containing water vapor or the like, a porous material of polyolefin or fluoropolyolefin, or a mixed solution of a poor solvent and a solvent.

The solution viscosity (30 캜) of the polyamic acid solution composition can be flexible in a film form and the viscosity at which the polyamic acid is precipitated can be suitably determined. From the viewpoints of flexibility and film strength, the solution viscosity (30 캜) is preferably 10 to 10000 poise (1 to 1000 Pa · s), more preferably 100 to 3000 poise (10 to 300 Pa · s) Preferably 200 to 2000 poises (20 to 200 Pa · s), particularly preferably 300 to 2000 poises (30 to 200 Pa · s). On the other hand, the solution viscosity (30 DEG C) was measured by the method described in the examples.

&Lt; Preparation of porous polyamic acid film >

The porous polyamic acid film can be obtained by making the film obtained by softening the polyamic acid solution composition (non-oriented) into contact with the poor solvent of the polyamic acid by, for example, dipping to make the film porous. It is possible to obtain a porous polyamic acid film after causing a phase separation phenomenon of polyamic acid by replacing a good solvent in the polyamic acid solution composition with a poor solvent and performing cleaning and / or drying as necessary.

The obtained porous polyamic acid film may be colored and imidized simultaneously by thermal imidization in which the film is subjected to cleaning and / or drying, if necessary, followed by heat treatment at 250 占 폚 or higher, to obtain a colored polyimide porous film. It is preferable that the colored polyimide porous film is colored in a black system to a brown system.

The film obtained by softening the polyamic acid solution composition (unleaded) can be obtained by (i) contacting one side or both sides of the film with a gas (for example, air or the like) containing water vapor or organic vapor such as alcohol before contact with a poor solvent (Contact time is preferably within 5 minutes, more preferably within 3 minutes, more preferably within 2 minutes), (ii) a polymerization solvent (which may include a poor solvent) on one side or both sides of the film ), Or (iii) a porous film such as polyolefin may be laminated on one or both sides of the film.

As the porous film which can be laminated on the film obtained by softening the polyamic acid solution composition, it is preferable to have the following properties.

(1) Easily peeled off from the polyamic acid to be precipitated.

(2) a polyamic acid solvent such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylacetamide (DMAc), and a solvent such as water and alcohol Permeable, has an appropriate affinity with these solvents, and has a structure in which holes having a diameter of 0.1 to several μm are dispersed at a sufficient density.

(3) At least one side has a smoothness higher than that required for the porous film to be produced.

(4) Stiffness that does not generate wrinkles when the polyamic acid solution is immersed.

As the porous film, a porous film made of polyolefin such as polyethylene or polypropylene, Teflon (registered trademark), or the like having a pore diameter of 0.1 to 5 mu m and a thickness of 10 to 100 mu m is suitably used.

(Poor solvent of polyamic acid)

As the poor solvent of the polyamic acid, those which are miscible with the polymerization solvent used for the polymerization of the polyamic acid can be used. Examples of the solvent include water, methanol, ethanol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-propyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, Ketones such as alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone, and aromatic solvents such as toluene and xylene.

Among them, water alone or a mixed solvent of water and a poor solvent such as an aliphatic alcohol having 1 to 3 carbon atoms such as methanol, ethanol, isopropyl alcohol, or a ketone having 3 to 6 carbon atoms is preferable from the viewpoints of safety and homogeneity of the resulting porous film .

The poor solvent may be a mixed solvent with a polymerization solvent used for polymerization of polyamic acid, if necessary.

When a mixed solvent of water and the organic solvent is used as the poor solvent, the content of water in the mixed solvent is preferably 5 mass% or more and less than 100 mass%, more preferably 20 mass% or more and less than 100 mass% Preferably 30 to 95% by mass, and particularly preferably 45 to 90% by mass. The content of the organic solvent (poor solvent) in the mixed solvent is preferably 0% by mass or more and 95% by mass or less, more preferably 0% by mass or more and 80% by mass or less, still more preferably 3% By mass to 5% by mass to 30% by mass.

The temperature of the poor solvent is usually -30 to 70 占 폚, preferably 0 to 60 占 폚, more preferably 10 to 50 占 폚.

(Porous polyamic acid film)

The porous polyamic acid film to be obtained can be suitably selected depending on the kind of the polyamic acid used, the solid content concentration of the polyamic acid solution, the solution viscosity of the polyamic acid solution composition, the organic solvent, the solidification conditions (temperature, The porosity, the average pore size, and the like can be appropriately adjusted.

According to the production method of the present invention, various types of porous polyamic acid films can be obtained. For example, typical porous polyamic acid films of the following (1) to (4) can be mentioned.

Form (1): A homogeneous porous film having no dense surface layer on both surfaces and substantially free of voids (large pores) in the film.

(2): A three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, wherein the macrovoid layer has a plurality of macroboids surrounded by the surface layer and a partition wall joined to the surface layer and a plurality of pores A porous film having a so-called honeycomb sandwich structure in which the pores and the macro void are communicated with each other.

In the case of producing the film of Form (2), the organic compound having a polar group is previously added to the polyamic acid solution composition in an amount of 1 to 150 parts by mass, preferably 10 to 100 parts by mass, Should be contained in an amount of 20 to 70 parts by mass. As the organic compound having a polar group, an organic compound having a carboxylic acid group such as benzoic acid or phthalic acid is preferable.

Form (3): A symmetric or asymmetric porous film having a dense surface layer on one side or both surfaces, and voids (large voids) in the inside of the film being substantially absent.

Form (4): A symmetric or asymmetric porous film having a dense surface layer on one surface or both surfaces, and a large number of voids (large pores) in the inside of the film.

Production of a colored polyimide porous film using the porous polyamic acid film of Forms (1) and (2) will be described later.

&Lt; Heat treatment of porous polyamic acid film &

The colored polyimide porous film of the present invention can be obtained by heat-treating the porous polyamic acid film at 250 캜 or higher.

In the heat treatment, in order to suppress adverse effects such as deterioration of the smoothness of the film due to heat shrinkage, for example, a part or whole of the end portion of the porous polyamic acid film, preferably both end portions or entire end portions , A pin, a chuck, or a pin roll, etc., and heating in air. The heating temperature is preferably 280 to 500 占 폚, more preferably 300 to 480 占 폚, and still more preferably 330 to 450 占 폚. The heating time can be appropriately selected, but is preferably 5 to 120 minutes, and more preferably 5 to 60 minutes. Imidation and / or coloring proceeds by this heat treatment.

The water generated in accordance with the imidization reaction can be removed from the reaction system together with the heating gas stream.

The polyimide constituting the obtained colored polyimide porous film preferably has an imidization ratio by IR measurement of preferably 70% or more, more preferably 80% or more, more preferably 85% or more, still more preferably 90% or more , And particularly preferably 95% or more.

On the other hand, the chemical imidization treatment may be performed before the heat treatment.

The chemical imidization is generally carried out at 20 to 200 캜, preferably 25 to 150 캜, more preferably 30 to 100 캜, in the presence of the catalyst and the dehydrating agent, from the viewpoints of the reaction rate, .

Examples of the catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine; aromatic tertiary amines such as dimethyl aniline; aromatic tertiary amines such as isoquinoline, pyridine, 2-methylpyridine, 3-methylpyridine, And heterocyclic tertiary amines such as imidazole and benzimidazole. Heterocyclic tertiary amines are preferable, and 3-methylpyridine, 4-methylpyridine, imidazole and benzimidazole are more preferable .

Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, aromatic acid anhydrides such as benzoic anhydride and phthalic anhydride, and the like, and aliphatic acid anhydrides are preferable, and acetic anhydride is more preferable.

According to the production method of the present invention, by using the above-mentioned porous polyamic acid film, colored polyimide porous films of the following two typical types can be produced.

<Form (A) Production of colored polyimide porous film>

(I) a protective solvent such as a polymerization solvent (which may contain a poor solvent) or the like is coated on one side or both sides of the above-mentioned film, and if necessary, left on the other side of the porous polyamic acid film Or (ii) a porous film such as polyolefin is laminated on one side or both sides of the film. Thereafter, the obtained laminate is brought into contact with the poor solvent of the polyamic acid by dipping or the like to make it porous. A porous polyamic acid film can be obtained after causing a phase separation phenomenon of polyamic acid by replacing a good solvent in the porous polyamic acid film with a poor solvent and performing cleaning and / or drying as necessary.

The obtained porous polyamic acid film is heat-treated at 250 캜 to obtain a colored polyimide porous film (form (A)).

The colored polyimide porous film of Form (A) is a homogeneous porous film having no dense surface layer on both surfaces and substantially free of voids (large voids) in the film. The thickness of the porous film is preferably 5 to 100 占 퐉, more preferably 10 to 80 占 퐉, and the average pore size is preferably 0.01 to 5 占 퐉, more preferably 0.02 to 2 占 퐉, More preferably 0.03 to 1 占 퐉, and the pores have a porous structure continuing in a nonlinear manner from one side to the other, and the porosity is preferably 15 to 80%, more preferably 20 to 80% And the Gurley value (air permeability) is preferably 30 to 1000 sec / 100 cc, more preferably 30 to 1000 sec / 100 cc, more preferably 30 to 100 cc, 120 sec / 100 cc.

<Form (B) Production of colored polyimide porous film>

(Ii) a method in which the porous polyamic acid film of the above-mentioned mode (2) (unleaded) is allowed to stand in the air or in the film obtained by softening the polyamic acid solution composition, (Iii) a porous film such as polyolefin is laminated on one side or both sides of the film. Thereafter, the obtained laminate is brought into contact with the poor solvent of the polyamic acid by dipping or the like to make it porous. It is possible to obtain a porous polyamic acid film after causing a phase separation phenomenon of polyamic acid by replacing a good solvent in the polyamic acid solution composition with a poor solvent and performing cleaning and / or drying as necessary.

The obtained porous polyamic acid film is heat-treated at 250 캜 to obtain a colored polyimide porous film (form (B)).

The colored polyimide porous film of Form (B) is a three-layered porous polyimide film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of Called microporous sandwich structure having macro voids and plural pores, wherein the pores and the macro voids are in communication with each other. The thicknesses of the surface layer and the macrovoid layer of the porous film are preferably 0.1 to 15 탆, more preferably 1 to 12 탆, and still more preferably 2 to 10 탆, More preferably 10 to 300 占 퐉, more preferably 20 to 100 占 퐉, and the average pore size of macroboid in the film plane direction is preferably 10 to 150 占 퐉, more preferably 10 to 100 占 퐉, The average pore size of the pores is preferably 0.01 to 5 占 퐉, more preferably 0.01 to 3 占 퐉, still more preferably 0.02 to 2 占 퐉, and the porosity is preferably 70 to 50 占 퐉, (Air permeability) is preferably 100 seconds or less / 100 cc, more preferably 80 seconds or less / 100 cc, still more preferably 95 to 90%, still more preferably 71 to 90% Preferably not more than 50 seconds / 100 cc.

The length (L) in the film plane direction and the length (d) in the film thickness direction of macrovoids having an average pore size of 10 mu m or more in the film plane direction in the section cut perpendicular to the film plane direction of the colored polyimide porous film, Is preferably at least 60%, more preferably at least 70%, and even more preferably from 73 to 100%.

Further, the film thickness change ratio after compression stress load at 250 캜 for 15 minutes and 0.5 MPa is preferably 5% or less, more preferably 3% or less, and further preferably 0 to 1%. Further, the dimensional stability in the film plane direction at 200 deg. C for 2 hours according to ASTM D1204 is preferably within +/- 1%.

On the other hand, the film thickness, the average pore size, the porosity and the gully value are measured by the method described in the embodiment.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. On the other hand, measurement of the solution viscosity of the polyamic acid solution composition and evaluation of the colored polyimide molded product (film) and the polyimide porous film were carried out by the following methods.

I-1. Measurement of solution viscosity of polyamic acid solution composition

The polyamic acid solution composition was placed in a sealed container and held in a thermostatic chamber at 30 캜 for 10 hours. The polyamic acid solution obtained was used as a measurement solution, and an E-type viscometer (manufactured by TOKYO KAGAKU CO., LTD., EHD type cone- Rotor: 1 ° 34 ') at a temperature of 30 ± 0.1 ° C. The measurement was carried out three times and the average value was adopted. When there was a gap of 5% or more in the measurement point, an additional 5 measurements were made and an average value of 5 points was adopted.

I-2. How to measure the intrinsic viscosity

The intrinsic viscosity number is the same as the intrinsic viscosity, and is the ratio of the reduced viscosity (the ratio of the relative viscosity increase r to the mass concentration c of the polymer to the ratio eta r / c) or the inherent viscosity (relative viscosity The ratio of the natural logarithm to the mass concentration c of the polymer).

The molecular weight can be determined from the intrinsic viscosity number by using the following Mark-Houwink equation (formula describing the molecular weight dependence of the intrinsic viscosity of the polymer).

[?] = K x M _r ^a

(Wherein M _r is usually one of molecular weights, and a is a constant determined uniquely by the type of polymer and solvent).

In the present invention, the polyamic acid is an unstable substance in the atmosphere, and it is difficult to obtain the molecular weight by means such as GPC. Therefore, an intrinsic viscosity number is used as an index of the molecular weight.

The measurement of the intrinsic viscosity number should be strictly conducted using a? Solvent and a lean solution in the? State, but the polyamic acid to be measured has a large interaction with the solvent molecules, making it difficult to prepare the? Solvent. In the case of polyamic acid, since the molecular weight can be calculated by the Mark-Hoinking formula even when both solvents are used for the measurement of the intrinsic viscosity, in the present invention, N-methyl-2-pyrrolidone (Hereinafter referred to as NMP) in the following procedure.

(1) An NMP solution of the polyamic acid to be measured was prepared so that the solution concentration c was 0.1, 0.075, 0.05, 0.025, and 0.010 [g / dL]. The solution was continuously stirred for one week in an anaerobic (anaerobic) atmosphere.

(2) The flow time of NMP in a thermostatic chamber at 30 ° C was measured using a Ubbelohde type dilution viscometer. Subsequently, the solution prepared in the above (1) was also subjected to the dropping time measurement. Any measurement was performed three times and the average value was adopted. When the difference in the measurement time was 3% or more, two additional measurements were further performed, and an average value of three points was taken from a small value to obtain the adopted value.

The specific viscosity ηsp was calculated from the measured values, and a graph was created with the y axis as ηsp / c and the x axis as c (Huggins plot). The plot points were analyzed by linear regression analysis with graph software to determine the number of extreme viscosities from the sections of the regression line. When the R2 of the regression line was 0.900 or less, the solution was again prepared and re-measured.

II. Evaluation of colored polyimide molded article (film) and polyimide porous film

(1) Thickness

The thickness of the porous film was measured using a contact thickness meter.

(2) Public rate

The film thickness and mass of the porous film cut to a predetermined size are measured, and the porosity is obtained from the basis weight by the following formula.

The porosity = S x d x D / w x 100

Where S is the area of the porous film, d is the film thickness, w is the measured mass, and D is the density of the polyimide. The density of the polyimide is 1.34 g / cm &lt; ^{3 &} gt ;.

(3) Gull value (specular degree)

The gurley value (the number of seconds required for 100 cc of air to permeate through the porous membrane under a pressure of 0.879 g / m ² ) was measured according to JIS P8117.

(4) Average pore size and maximum pore size

The hole area was measured with respect to the openings of not less than 200 points by scanning electron micrographs of the surface of the porous film, and from the average value of the hole areas, the following equation was established: Sa is the average value of the hole areas Therefore, the average pore diameter was calculated by assuming that the pore shape is the origin.

Average pore diameter = 2 占 Sa /? ^1/2

In addition, the diameter of the hole shape was calculated from the hole area, and the maximum value was set as the maximum hole diameter.

(5) Glass transition temperature

The dynamic viscoelasticity measurement was performed under the conditions of a tensile mode, a frequency of 10 Hz, a strain of 2% and a nitrogen gas atmosphere using a solid viscoelasticity analyzer, and the temperature at which the loss tangent is maximum in the temperature dispersion profile was defined as the glass transition temperature.

(6) Dimensional stability

Dimensional stability in the film plane direction under the conditions of 200 占 폚 and 2 hours in accordance with ASTM D1204 was measured.

(7) Film thickness change rate after compressive stress load

The film to be measured is cut into a square of 3 cm square, and the film thickness is measured with a contact type thickness meter by marking in a lattice shape at nine points. Next, the film to be measured is compressed under the conditions of 250 占 폚, 15 minutes, and 0.5 MPa using a high-precision hot press having a parallelism of less than 占 10 占 퐉 and a compression half-life of 占 占 占 占. Subsequently, after the film is allowed to stand on an SUS plate at room temperature for 30 minutes, the film thickness of the display portion is measured with a contact type film thickness meter. The percentage change in film thickness before and after compression at 9 points was determined by the following equation. The average value of 9 points was defined as the film thickness change rate.

Film thickness change rate (%) = [1 - [(film thickness after compression) / (film thickness before compression)]] × 100

(8) Total light transmittance (%) and turbidity (haze)

The total light transmittance and turbidity (haze) of the film were measured using a haze meter (trade name: NDH5000, manufactured by Nippon Kogyo Kogyo Co., Ltd.) conforming to JIS K7361, 7136 and 7105 and ASTM D1003.

(9) Color

The hue of the colored polyimide molded product (film) was measured under the transmission condition with respect to the plane of the measured product using a spectral side colorimeter (trade name: Color Robo III, manufactured by Color Techno Systems Co., Ltd.). During the measurement, measurement was carried out through a neutralization filter.

The hue of the polyimide porous film was measured using a spectroscopic colorimeter (manufactured by Color Techno System Co., Ltd., trade name: Color Robo III) at a light transmission angle of 45 degrees with respect to the plane of the measurement object. The film to be measured was placed on a white body, and measurement was carried out.

The results are numerically expressed by the L * a * b * colorimetric system (where L * represents brightness, a * represents chromaticity in the red-green direction, and b * represents the chromaticity in the yellow-blue direction).

Reference Example 1

The thermogravimetric reduction rate when the pellets of a polyacrylonitrile copolymer (trade name: Barex 2090S, hereinafter also referred to as "PAN") made by Mitsui Chemicals Inc. was heated at a rate of 5 ° C / minute from room temperature under an air atmosphere was measured Respectively. The results are shown in Fig. As a result, a slight weight loss was observed from about 250 ° C, and it was found that a weight loss of about 0.2% at 280 ° C, about 0.5% at 290 ° C, about 2% at 300 ° C and about 8% I could. These weight reductions are believed to be attributable to the progress of carbonization in such a manner that the cleavage and cross-linking reaction in the polyacrylonitrile molecules progress simultaneously.

From the above results, it can be seen that PAN can be preferably used as a coloring precursor in the present invention, and when PAN is used as a coloring precursor in the present invention, it is 250 DEG C or higher, preferably 280 DEG C or higher, more preferably 300 Lt; 0 &gt; C or more.

Preparation Example 101 (Preparation of polyamic acid solution composition A1)

In a 500 ml separable flask, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) was added as a tetracarboxylic acid component and N-methylpyrrolidone (NMP) Diaminodiphenylether (DADE) was weighed in an amount such that the molar ratio was 1 and the polymer concentration was 6 mass%, and polymerization reaction was carried out at 30 占 폚 for 28 hours to obtain a polyamic acid solution. This polyamic acid solution had a solid content concentration of 6 mass% and an intrinsic viscosity of 3.5.

Five parts by mass of PAN (manufactured by Mitsui Chemicals, Inc., trade name: Barex 2090S) was added to 100 parts by mass of the obtained polyamic acid. Thereafter, the resultant was covered with a separable cover equipped with a stirring blade, a nitrogen introduction pipe and an exhaust pipe, and stirring was started. After 20 hours, 0.5 part by mass of 3,3 ', 4,4'-biphenyltetracarboxylic acid (BPDA) was added to 100 parts by mass of the polyamic acid, and the stirring operation was continued. Stirring was terminated after 40 hours, and the dope in the flask was filtered with a pressure filter (filter paper No. 60 for viscous liquid) made by ADVANTIC TONYANG CO., LTD.) To obtain polyamic acid solution composition A1. The solution was a viscous suspension liquid, and the solution viscosity was 410 poise (30 占 폚).

Preparation Example 102 (Preparation of polyamic acid solution composition B1)

A polyamic acid solution composition B1 was obtained in the same manner as in Preparation Example 101 except that PAN was not added. The solution was a viscous liquid and the solution viscosity was 400 poise (30 占 폚).

Preparation Example 201 (Preparation of polyamic acid solution composition A2)

In a 500 ml separable flask, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) was added as a tetracarboxylic acid component and N-methylpyrrolidone (NMP) Diaminodiphenylether (DADE) was weighed in an amount such that the molar ratio was 1 and the polymer concentration was 6 mass%, and polymerization reaction was carried out at 30 占 폚 for 28 hours to obtain a polyamic acid solution. The polyamic acid solution had an intrinsic viscosity number of 3.8 and a solid content concentration of 6 mass%.

Five parts by mass of PAN (manufactured by Mitsui Chemicals, Inc., trade name: Barex 2090S) was added to 100 parts by mass of the obtained polyamic acid. Thereafter, the resultant was covered with a separable cover equipped with a stirring blade, a nitrogen introduction pipe and an exhaust pipe, and stirring was started. After 20 hours, 30 parts by mass of benzoic acid and 1 part by mass of 3,3 ', 4,4'-biphenyltetracarboxylic acid were added to 100 parts by mass of the polyamic acid, and the stirring operation was continued. Stirring was terminated after 40 hours, and the dope in the flask was filtered through a pressure filter (Advanit Touyen Co., Ltd., filter paper No. 60 for viscous liquid) to obtain polyamic acid solution composition A2. The solution was a viscous suspension liquid, and the solution viscosity was 430 poise (30 占 폚). The results are shown in Table 1.

Preparation Examples 202 to 204 (Preparation of polyamic acid solution composition B2, C2, D2)

The polyamic acid solution compositions B2, C2 and D2 were obtained in the same manner as in Preparation Example 201 except that the addition amount of PAN was changed as shown in Table 1. The solution was a viscous suspension liquid.

Preparation Example 205 (Preparation of polyamic acid solution composition E2)

In Preparation Example 201, 5 parts by mass of ferrocene (manufactured by Wako Pure Chemical Industries, Ltd.), 30 parts by mass of benzoic acid and 1 part by mass of 3,3 ', 4,4'-biphenyltetracarboxylic acid were added to 100 parts by mass of polyamic acid The procedure of Preparation Example 201 was repeated to give a polyamic acid solution composition E2. The solution was a viscous liquid and the solution viscosity was 460 poise (30 占 폚).

Preparation Example 206 (Preparation of polyamic acid solution composition F2)

A polyamic acid solution composition F2 was obtained in the same manner as in Preparation Example 201 except that PAN was not added. The solution was a viscous liquid, and the solution viscosity was 390 poise (30 占 폚).

Preparation Example 207 (Preparation of polyamic acid solution composition G2)

A polyamic acid solution composition G2 was obtained in the same manner as in Preparation Example 203 except that benzoic acid was not added. The solution was a viscous liquid and the solution viscosity was 450 poise (30 占 폚).

Preparation Example 208 (Preparation of polyamic acid solution composition H2)

A polyamic acid solution composition H2 was obtained in the same manner as in Preparation Example 207 except that PAN was not added. The solution was a viscous liquid and the solution viscosity was 425 poise (30 占 폚).

Example 101 (Production of polyimide film)

The polyamic acid solution composition A1 obtained in Preparation Example 101 was uniformly and flexibly coated at a thickness of about 300 占 퐉 on a 20 cm square stainless steel substrate subjected to mirror polishing on the surface using a table automatic coater at room temperature. Thereafter, the entire substrate was placed in a hot air furnace, and heated to 360 DEG C at an average temperature elevation rate of 10 DEG C / minute, maintained as it was for 5 minutes, and then slowly cooled. The substrate was taken out of the hot air, and the cutter knit was cut around the four sides of the film adhered to the substrate, and then immersed in pure water for 24 hours per substrate. The polyimide film naturally peeled off from the substrate was dried at a temperature of 100 占 폚 to obtain a polyimide film having a thickness of 20 占 퐉. This film was dark brown. Table 2 shows the results of measurement of total light transmittance, turbidity and color of the polyimide film.

Comparative Example 101 (Production of polyimide film)

A polyimide film was obtained in the same manner as in Example 101 except that the polyamic acid solution composition B1 obtained in Preparation Example 102 was used. The obtained film was deep yellow, transparent, and had a thickness of 21 mu m. Table 2 shows the results of measurement of total light transmittance, turbidity and color of the polyimide film.

From Table 2, it can be seen that in Example 101, coloration was appropriately performed and the light transmittance was effectively suppressed.

Example 201

The polyamic acid solution composition A2 obtained in Preparation Example 201 was uniformly and flexibly coated at a thickness of about 120 占 퐉 on a stainless steel 20 cm square substrate whose surface was mirror-polished using a table automatic coater at room temperature. Thereafter, the substrate was left in an atmosphere of a temperature of 23 DEG C and a humidity of 40% for 90 seconds, and then the entire substrate was immersed in a poor solvent of polyamic acid (80 mass% of water and 20 mass% of NMP) at room temperature. After immersion, the substrate was allowed to stand for 8 minutes to deposit a polyamic acid film on the substrate. Thereafter, the substrate was taken out from the bath, and the polyamic acid film deposited on the substrate was peeled off. Then, the substrate was immersed in pure water for 3 minutes and dried in an atmosphere at a temperature of 23 캜 and a humidity of 40% to obtain a polyamic acid film . On the other hand, a part of the polyamic acid film was sampled to perform color measurement. The results of color measurement of the polyamic acid film are shown in Table 3.

The polyamic acid membrane was attached to a 10 cm square pin tenter and set in a hot air furnace. The polyimide porous film was heated to a temperature of 360 DEG C at a temperature raising rate of about 10 DEG C / min and then heat-treated at a temperature profile maintained for 10 minutes.

The obtained polyimide porous film had a film thickness of 32 탆, a porosity of 79%, and a gluing value of 22 sec / 100 cc.

The surface of the polyimide porous film was observed with a scanning electron microscope. The surface of the polyimide porous film had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.19 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 290 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Examples 202 to 205

A polyimide porous film was obtained in the same manner as in Example 201 except that the polyamic acid solution compositions B2 to E2 obtained in Preparation Examples 202 to 205 were used. Table 3 shows the film thickness, porosity and gelling value of the obtained polyimide porous film. All membranes were dark brown to black and opaque.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. The surface of the polyimide porous membrane had a porous structure having many holes communicating with the substrate side. The average pore size of the surface was in the range of 0.15 to 0.20 mu m and the maximum pore size was 10 mu m or less . In addition, a plurality of macrovoids exist in the cross section of the polyimide porous film, and the number of voids in which the ratio (L / d) falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other. For all the polyimide porous films, the dimensional stability was within 1% at 200 캜, and the film thickness change rate after the compression stress loading was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 206

The polyamic acid solution composition G2 obtained in Preparation Example 207 was uniformly and flexibly coated at a thickness of about 250 占 퐉 on a stainless steel 20 cm square substrate whose surface was mirror polished by using a table automatic coater under a room temperature. On the polyamic acid solution coated on the substrate, NMP was uniformly applied as a protective solvent layer using a doctor knife having an interval of 100 mu m with respect to the liquid surface of the polyamic acid solution, and left standing for 1 minute. Thereafter, the substrate was left in an atmosphere at a temperature of 23 DEG C and a humidity of 40% for 90 seconds, and a poor solvent of polyamic acid (90 mass% methanol, 5 mass% water and 5 mass% NMP) was immersed in the entire substrate at room temperature. After immersion, the substrate was allowed to stand for 10 minutes to deposit a polyamic acid film on the substrate. Thereafter, the substrate was taken out from the bath, and the polyamic acid film deposited on the substrate was peeled off, then immersed in pure water for 3 minutes, and dried in an atmosphere at a temperature of 23 캜 and a humidity of 40% to obtain a polyamic acid film. A part of the polyamic acid film was sampled to perform color measurement. The results of color measurement of the polyamic acid film are shown in Table 3.

The polyamic acid membrane was attached to a 10 cm square pin tenter and set in a hot air furnace. The polyimide porous film was heated to a temperature of 360 DEG C at a temperature raising rate of about 10 DEG C / min and then heat-treated at a temperature profile maintained for 10 minutes.

The obtained polyimide porous film was dark brown to black and opaque, and had a film thickness of 29 탆, a porosity of 48% and a gluing value of 78 sec / 100 cc.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. Both surfaces of the polyimide were in a network structure connected in a network. The average pore size of the surface was 0.17 mu m and the maximum pore size was 1.6 mu m. The cross section of the polyimide porous film was a porous structure in which the polyimide and the void were continuously and homogeneously connected together, and voids having a length of 1 mu m or more in the film transverse direction were not observed. That is, the obtained film is a uniform film having no dense layer on both surfaces, and has a hole having an average pore diameter of 0.01 to 5 占 퐉 on one surface or both surfaces thereof, and the hole has a nonporous continuous porous Structure.

The glass transition temperature of the polyimide porous film was about 280 ° C and the dimensional stability was within 1% at 200 ° C. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 207

The polyamic acid solution composition B2 obtained in Preparation Example 202 was uniformly and flexibly coated to a thickness of about 120 占 퐉 on a stainless steel 20 cm square substrate whose surface was mirror polished by using a desk automatic coater at room temperature. Thereafter, the substrate was left in an atmosphere of a temperature of 23 DEG C and a humidity of 40% for 90 seconds, and then the entire substrate was immersed in a poor solvent of polyamic acid (80 mass% of water and 20 mass% of NMP) at room temperature. After immersion, the substrate was allowed to stand for 8 minutes to deposit a polyamic acid film on the substrate. Thereafter, the substrate was taken out from the bath, and the polyamic acid film deposited on the substrate was peeled off, then immersed in pure water for 3 minutes, and dried in an atmosphere at a temperature of 23 캜 and a humidity of 40% to obtain a polyamic acid film. On the other hand, a part of the polyamic acid film was sampled to perform color measurement. The results of color measurement of the polyamic acid film are shown in Table 3.

The polyamic acid film was attached to a 10 cm square pin tenter and set in a hot air furnace. Heated to 280 DEG C at a temperature raising rate of about 10 DEG C / min, and then heat-treated at a temperature profile maintained for 10 minutes to obtain a polyimide porous film.

The obtained polyimide porous film had a film thickness of 33 탆, a porosity of 80%, and a gelling value of 56 sec / 100 cc.

 The surface of the polyimide porous membrane was observed with a scanning electron microscope. The surface of the polyimide porous membrane had a porous structure having many holes communicating with the substrate. The average pore size of the porous polyimide membrane was 0.16 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 275 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 208

A polyimide porous film was obtained in the same manner as in Example 207 except that the maximum temperature of the heat treatment was 300 占 폚. The obtained polyimide porous film had a film thickness of 33 탆, a porosity of 79%, and a gluing value of 41 sec / 100 cc.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. The surface of the polyimide porous membrane had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.17 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 280 ° C and the dimensional stability was within 1% at 200 ° C. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 209

A polyimide porous film was obtained in the same manner as in Example 207 except that the maximum temperature of the heat treatment was 400 占 폚. The obtained polyimide porous film had a film thickness of 31 탆, a porosity of 76% and a gluing value of 31 sec / 100 cc.

The surface of the polyimide porous film was observed with a scanning electron microscope. The surface of the polyimide porous film had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.18 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 290 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 210

A polyimide porous film was obtained in the same manner as in Example 207 except that the solution used was changed to the polyamic acid solution composition C2 obtained in Preparation Example 203. [ The obtained polyimide porous film had a film thickness of 34 탆, a porosity of 81%, and a gelling value of 53 sec / 100 cc.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. The surface of the polyimide porous membrane had a porous structure having many holes communicating with the substrate. The average pore size of the porous polyimide membrane was 0.16 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 275 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 211

A polyimide porous film was obtained in the same manner as in Example 208 except that the solution used was changed to the polyamic acid solution composition C2 obtained in Preparation Example 203. [ The obtained polyimide porous film had a film thickness of 32 탆, a porosity of 80% and a gluing value of 38 sec / 100 cc.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. The surface of the polyimide porous membrane had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.17 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 285 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Example 212

A polyimide porous film was obtained in the same manner as in Example 209 except that the solution used was changed to the polyamic acid solution composition C2 obtained in Preparation Example 203. [ The obtained polyimide porous film had a film thickness of 31 탆, a porosity of 78%, and a gluing value of 28 sec / 100 cc.

The surface of the polyimide porous film was observed with a scanning electron microscope. The surface of the polyimide porous film had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.18 mu m and the maximum pore size was 10 mu m or less. In addition, a plurality of macro voids exist in the cross section of the polyimide porous film, and many macroboids having a length of 10 mu m or longer in the film lateral direction can be confirmed. Of the voids having a length of 5 mu m or more in the width direction, The number of voids in which the ratio (L / d) of the length d in the film thickness direction falls within the range of 0.5 to 3 was 75% or more. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other.

The glass transition temperature of the polyimide porous film was about 290 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

Comparative Example 201

A polyimide porous film was obtained in the same manner as in Example 201 except that the polyamic acid solution composition F2 obtained in Preparation Example 206 was used. The resulting film was light yellow and opaque. Table 3 shows the film thickness, porosity and gelling value of the obtained polyimide porous film.

The surface of the polyimide porous film was observed with a scanning electron microscope. The surface of the polyimide porous film had a porous structure having many holes communicating with the substrate. The average pore size of the surface was 0.18 mu m and the maximum pore size was 10 mu m or less. The ratio of the length (L) in the transverse direction to the length (d) in the film thickness direction among the voids having a length of 5 mu m or more in the transverse direction of the polyimide porous film is L / d = The number of voids in the range of 3 was more than 75%. That is, the obtained porous film is a three-layer porous film having two surface layers and a macrovoid layer sandwiched therebetween, and the macrovoid layer has a plurality of macrovoids surrounded by the surface layer and the barrier ribs bonded to the surface layer, And that the pores and the macrovoids communicate with each other. In addition, the dimensional stability of the polyimide porous film was within 1% at 200 占 폚, and the film thickness change rate after the compression stress load was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color.

Comparative Example 202

A polyimide porous film was obtained in the same manner as in Example 206 except that the polyamic acid solution composition H obtained in Preparation Example 208 was used. The obtained film was light yellow and opaque, and had a film thickness of 30 탆, a porosity of 48% and a gluing value of 69 sec / 100 cc.

The surface of the polyimide porous membrane was observed with a scanning electron microscope. Both surfaces of the polyimide were in a network structure connected in a network. The average pore size of the surface was 0.17 mu m and the maximum pore size was 1.7 mu m. The cross section of the polyimide porous film was a porous structure in which the polyimide and the void were continuously and homogeneously connected together, and voids having a length of 1 mu m or more in the film transverse direction were not observed. That is, the obtained film is a uniform film having no dense layer on both surfaces, and has a hole having an average pore diameter of 0.01 to 5 占 퐉 on one surface or both surfaces thereof, and the hole has a nonporous continuous porous Structure.

The glass transition temperature of the polyimide porous film was about 285 캜, and the dimensional stability was within 1% at 200 캜. The rate of change in film thickness after compression stress loading at 250 占 폚 for 15 minutes and 0.5 MPa was 1% or less. Table 3 shows the results of measurement of total light transmittance, turbidity and color of the polyimide porous film.

From Table 3, it can be seen that, in Examples 201 to 212, the polyamic acid before the thermal imidization treatment was not colored, but the coloring was appropriately performed by the thermal imidization treatment and the light transmittance was effectively suppressed. In addition, it is understood that the structure and function of the porous film are colored without being damaged, considering Comparative Examples 201 and 202 as well.

The colored polyimide molded article of the present invention can be used as a material for electronic parts or electronic devices such as a printed wiring board, a flexible printed board, a TAB tape, a COF tape, a cover film, a reinforcing film, , And the like. The colored polyimide porous film of the present invention can be used in various fields requiring heat resistance, light shielding property, antistatic property, thermal conductivity, and the like, for example, an interlayer insulating film for a multilayer substrate, a liquid crystal alignment film, a color filter protective film, And the like.

Claims (10)

A polyamic acid solution composition containing at least a solution of a polyamic acid obtained from a tetracarboxylic acid component and a diamine component and a coloring precursor or a polyimide solution composition containing a polyimide solution and a coloring precursor and then heat- Wherein the method comprises the steps of:
Wherein the coloring precursor is at least one selected from the group consisting of a polymer obtained from a monomer containing acrylonitrile and a ferrocene compound. The method according to claim 1,
Wherein the tetracarboxylic acid component is at least one member selected from the group consisting of biphenyltetracarboxylic acid dianhydride and pyromellitic acid dianhydride, and the diamine component is at least one member selected from the group consisting of paraphenylenediamine, diaminodiphenylether and bis Cis) benzene. &Lt; / RTI &gt; delete The method according to claim 1,
Wherein the polyamic acid solution composition or the polyimide solution composition is a suspension or a transparent uniform solution. The method according to claim 1,
A step of dipping a film obtained by casting the polyamic acid solution composition into a poor solvent of polyamic acid to prepare a porous polyamic acid film, and a step of heat-treating the porous polyamic acid film at 250 ° C or higher , And the colored polyimide formed body is a colored polyimide porous film. 6. The method of claim 5,
Wherein the poor solvent is a mixed solvent containing water or water. The method according to claim 1,
Wherein the heat treatment is carried out at 280 to 500 占 폚 for 5 to 60 minutes in the atmosphere while the molded article molded using the polyamic acid solution composition or the polyimide solution composition is fixed. A colored polyimide molded article obtained by the method according to any one of claims 1, 2, and 4 to 7. 9. The method of claim 8,
Wherein the film has a uniform film thickness of 5 to 100 占 퐉 without a dense layer on both surfaces and has a hole with an average pore diameter of 0.01 to 5 占 퐉 on one surface or both surfaces thereof, A colored polyimide formed body having a non-linear continuous porous structure, a porosity of 15 to 80%, and a Gurley value of 30 to 1000 sec / 100 cc. 9. The method of claim 8,
Layer structure having two surface layers and a macrovoid layer sandwiched therebetween, wherein the macrovoid layer has a plurality of macroboids surrounded by the surface layer and a partition wall joined to the surface layer and a plurality of pores, A colored polyimide molded article having a structure in which macro voids communicate with each other.

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